CN103657707A - Preparation method of low carbon hydrocarbon aromatization catalyst - Google Patents
Preparation method of low carbon hydrocarbon aromatization catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method of a low carbon hydrocarbon aromatization catalyst, and mainly solves the problem that the stability of a hydrocarbon aromatization catalyst reaction in the prior art is not good. The preparation method provided by the invention comprises the following steps of (a) kneading and forming 50-90 parts of a ZSM-5 molecular sieve and 10-50 parts of a binding agent so as to obtain a forming catalyst precursor I; (b) treating a mixture I with vapor for 0.1-40 hours under the normal pressure at the temperature of 200-700 DEG C and at airspeed of 0.1-20h<-1> so as to obtain a precursor II; (c) placing the precursor II in an acid solution the concentration of which is 0.1-5 mol/L, and treating the precursor II for 1-24 hours at 20-95 DEG C so as to obtain a precursor III; (d) loading the precursor III with at least one of VIII, IIB or IIIA group through an impregnation method so as to obtain the low carbon hydrocarbon aromatization catalyst, wherein the loading capacity is 0.1-10% of the weight of the precursor III. According to the technical scheme, the preparation method provided by the invention solves the problem in the prior art and can be used for preparing industrial production of the low carbon hydrocarbon aromatization catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of aromatization of low carbon hydrocarbon catalyst.
Background technology
Aromatic hydrocarbons is widely used in synthetic fibers, synthetic resin, synthetic rubber and various fine chemicals, is indispensable basic organic chemical industry raw material; In addition non-benzene aromatic hydrocarbons is still produced the important mediation component of high-knock rating gasoline.In recent years, aromatic hydrocarbons downstream product development rapidly, causes the demand sustainable growth of domestic and international market to aromatic hydrocarbons, wherein China to aromatic hydrocarbons year the growth rate of demand more than 10%.
C4 ~ C6 lower carbon number hydrocarbons and the hydrocarbon mixture that contains C4 ~ C6 lower carbon number hydrocarbons are the secondary liquid of petrochemical industry and oil refining industry, originate from ethylene project, oil plant and natural gas purification process.In numerous low-carbon (LC) hydro carbons, except minority component is used as industrial chemicals by extracting, very major part is all used as cheap fuel, and main cause is that fuel price is higher.Along with the smooth enforcement of China's strategy to develop western regions and West-East National Gas Transmission Project, and from the extensive use of coal dimethyl ether synthesis technology, lower carbon number hydrocarbons is extruded commercial market gradually by more cheap fuel such as pipe natural gas at last.These low-carbon (LC) hydro carbons are converted into aromatic hydrocarbons by technology of aromatization, not only can be aromatic hydrocarbons production and open up new raw material source, and can optimize and utilize lighter hydrocarbons resource, improve petroleum chemical enterprise's economic benefit.
At present the research of aromatization of low carbon hydrocarbon is mainly concentrated on molecular sieve catalyst, particularly ZSM-5 molecular sieve.Patent CN101530813A discloses a kind of molecular sieve catalyst preparation method for carbon 4 liquid gas aromatization reaction, and adopting rare earth-ZSM-5/ZSM-11 cocrystallization molecular sieve is parent, through making catalyst after alkali treatment-steam treatment-zinc supported.At 470 ~ 520 ℃, pressure 0.3 ~ 0.9MPa, weight space velocity 0.5 ~ 1.5 hour
-1reaction condition under, catalyst single pass life is investigated the 30th hour, aromatics yield is 62 about % by weight.
Patent CN1586721A discloses a kind of molecular sieve catalyst preparation method for carbon four liquefied petroleum gas aromatisation, and the silica-rich zeolite that employing grain size is 10 ~ 500nm, carries out steam treatment and organic acid reaming modification makes catalyst, does not add metal component.400 ℃, pressure 3MPa, weight space velocity 0.8 hour
-1reaction condition under, catalyst single pass life is investigated the 10th day, aromatics yield is 49 about % by weight.
Patent CN1232071A discloses and a kind ofly Zn, rare earth, ZSM-5 and aluminium oxide, has consisted of, and has carried out the aromatized catalyst preparation method of steam treatment modification, and wherein Zn species are by [Zn (NH
3)
4]
2+form be introduced into molecular sieve catalyst.This catalyst is at 520 ~ 550 ℃, mass space velocity 0.6 ~ 1.5 hour
-1reaction condition under to mixing carbon four, carry out aromatization, it is 300 ~ 450 hours that aromatics yield is greater than 40% one way duration of runs.
Patent CN1340601A discloses and a kind ofly ZnO, ZSM-5 molecular sieve, aluminium oxide and VA or group vib oxide, has consisted of, and has carried out the aromatized catalyst preparation method of steam treatment modification, for n-hexane with mix the aromatization of carbon four.This catalyst is at 450 ~ 600 ℃, pressure 0.1-1.0MPa, mass space velocity 0.2 ~ 12 hour
-1reaction condition under to mixing carbon four, carry out aromatization, it is 470 hours that aromatics yield is greater than 41% one way duration of runs.
In above-mentioned technology, the single pass life of catalyst, all in 500 hours, shows that the reaction stability of catalyst is undesirable, and this causes reactor in course of reaction to switch regeneration frequently.
Summary of the invention
Technical problem to be solved by this invention is the bad problem of aromatized catalyst reaction stability in prior art, and a kind of preparation method of new aromatization of low carbon hydrocarbon catalyst is provided.Catalyst prepared by the method, for aromatization of low carbon hydrocarbon reaction, has good reactivity and stability.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of aromatization of low carbon hydrocarbon catalyst, comprises the following steps:
A) 50 ~ 90 parts of ZSM-5 molecular sieves and 10 ~ 50 parts of binding agents are kneaded and formed, obtain preformed catalyst precursor mixture I;
B) by mixture I, in normal pressure, temperature, be that 200 ~ 700 ℃, air speed are 0.1 ~ 20 hour
-1water Under steam treated 0.1 ~ 40 hour, obtains precursor II;
C) precursor II being placed in to the acid solution that concentration is 0.1 ~ 5 mol/L, is to process 0.1 ~ 24 hour under 20 ~ 95 ℃ of conditions in temperature, obtains precursor III;
D) by infusion process, to the load of precursor III, be selected from least one element in VIII, IIBHuo IIIA family, obtain described aromatization of low carbon hydrocarbon catalyst; Wherein, load capacity is 0.1 ~ 10% of precursor III weight.
In technique scheme, described binding agent preferred version is at least one being selected from aluminium oxide or boehmite.Steam treatment temperature preferable range is 300 ~ 600 ℃, and air speed preferable range is 1 ~ 18 hour
-1, processing time preferable range is 1 ~ 30 hour.Described sour preferred version is at least one being selected from oxalic acid or nitric acid.The concentration preferable range of acid solution is 0.2 ~ 4 mol/L, and acid treatment temperature preferable range is 30 ~ 85 ℃, and time preferable range is 1 ~ 20 hour.VIII family element preferred version is at least one being selected from Fe, Co or Ni, and IIB family element preferred version is at least one being selected from Zn or Cd, and IIIA family element preferred version is at least one being selected from Al or Ga.The load capacity preferable range that is selected from least one element in VIII, IIBHuo IIIA family is 0.5 ~ 8% of precursor III weight.The silica alumina ratio SiO of ZSM-5 molecular sieve
2/ Al
2o
3be 20 ~ 300.
Catalyst prepared by the present invention reacts for aromatization of low carbon hydrocarbon, generates the aromatic product containing benzene,toluene,xylene.Reaction condition is: 400 ~ 600 ℃ of reaction temperatures, and preferable range is 450 ~ 550 ℃; Reaction pressure 0 ~ 2.0MPa, preferable range is 0.1 ~ 1.0MPa; Weight space velocity 0.01 ~ 10 hour
-1, preferable range is 0.3 ~ 5 hour
-1.Lower carbon number hydrocarbons described in the inventive method refers to C4 ~ C6 lower carbon number hydrocarbons, and wherein the percentage by weight of each component is: monoolefine content 20 ~ 80%, and diolefin content is lower than 2%, and surplus is alkane.
Steam treatment is the acid method of adjustment that aromatized catalyst is conventional, but the non-framework aluminum producing in this process easily causes the obstruction of molecular sieve pore passage, thereby affects catalyst reaction performance.By suitable acid treatment, can dissolve part non-framework aluminum, dredging molecular sieve pore passage, improves the steam treatment mass transfer diffusion of molecular screen material afterwards.Introduce afterwards one or more metal species and adjust the acids type distribution on molecular sieve, suppress the carbon distribution speed on catalyst, and then realization obtains more excellent reaction stability when guaranteeing aromatization of low carbon hydrocarbon reactivity.The prepared catalyst of the present invention can show preferably reactivity and stability in aromatization of low carbon hydrocarbon course of reaction, when adopting C4 ~ C6 mixing lower carbon number hydrocarbons to make raw material, catalyst single pass life reaches 700 hours, aromatics yield 48 % by weight, can alleviate in existing commercial fixed bed device that reactor switches and catalyst regeneration problem frequently.
Below by comparative example and embodiment, the present invention is further elaborated.
The specific embodiment
[comparative example 1]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 20) is removed to template for 4 hours 550 ℃ of roastings.Resulting materials mixes with 1:0.5 part by weight with boehmite.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials is after ammonia exchange, 300 ℃, air speed 10 hours
-1water Under steam treated 15 hours, make catalyst.
[comparative example 2]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 20) is removed to template for 4 hours 550 ℃ of roastings.Resulting materials mixes with 1:0.5 part by weight with boehmite.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials is after ammonia exchange, 300 ℃, air speed 10 hours
-1water Under steam treated 15 hours.By incipient impregnation normal direction matrix material load Zn metal species, load capacity is 5% of matrix material weight, makes catalyst.
[embodiment 1]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 20) is removed to template for 4 hours 550 ℃ of roastings.Resulting materials mixes with 1:0.5 part by weight with boehmite.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials is after ammonia exchange, 300 ℃, air speed 10 hours
-1water Under steam treated 15 hours.Resulting materials in the oxalic acid solution of 1.0mol/L 80 ℃ process 6 hours.By incipient impregnation normal direction matrix material load Zn metal species, load capacity is 5% of matrix material weight, makes catalyst.
[comparative example 3]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 100) is removed to template for 4 hours 550 ℃ of roastings.Resulting materials mixes with 1:0.4 part by weight with boehmite.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials is after ammonia exchange, 400 ℃, air speed 8 hours
-1water Under steam treated 10 hours, make catalyst.
[comparative example 4]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 100) is removed to template for 4 hours 550 ℃ of roastings.Resulting materials mixes with 1:0.4 part by weight with boehmite.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials is after ammonia exchange, 400 ℃, air speed 8 hours
-1water Under steam treated 10 hours.By incipient impregnation normal direction matrix material load Ni metal species, load capacity is 1% of matrix material weight, makes catalyst.
[embodiment 2]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 100) is removed to template for 4 hours 550 ℃ of roastings.Resulting materials mixes with 1:0.4 part by weight with boehmite.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials is after ammonia exchange, 400 ℃, air speed 8 hours
-1water Under steam treated 10 hours.Resulting materials in the salpeter solution of 2.0mol/L 30 ℃ process 15 hours.By incipient impregnation normal direction matrix material load Ni metal species, load capacity is 1% of matrix material weight, makes catalyst.
[comparative example 5]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 150) is removed to template for 4 hours 550 ℃ of roastings.Resulting materials mixes with 1:0.3 part by weight with aluminium oxide.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials is after ammonia exchange, 600 ℃, air speed 4 hours
-1water Under steam treated 4 hours, make catalyst.
[comparative example 6]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 150) is removed to template for 4 hours 550 ℃ of roastings.Resulting materials mixes with 1:0.3 part by weight with aluminium oxide.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials is after ammonia exchange, 600 ℃, air speed 4 hours
-1water Under steam treated 4 hours.By incipient impregnation normal direction matrix material load Al and Ga metal species, load capacity is respectively 0.8% and 0.5% of matrix material weight, makes catalyst.
[embodiment 3]
NaZSM-5 molecular screen primary powder (silica alumina ratio is 150) is removed to template for 4 hours 550 ℃ of roastings.Resulting materials mixes with 1:0.3 part by weight with aluminium oxide.In mixture, add salpeter solution, pinch even and extruded moulding, pelletizing after dry and roasting.Resulting materials is after ammonia exchange, 600 ℃, air speed 4 hours
-1water Under steam treated 4 hours.Resulting materials in the mixed solution that contains 0.5mol/L nitric acid and 0.5mol/L oxalic acid 50 ℃ process 10 hours.By incipient impregnation normal direction matrix material load Al and Ga metal species, load capacity is respectively 0.8% and 0.5% of matrix material weight, makes catalyst.
[embodiment 4]
Catalyst performance examination is carried out on fixed-bed reactor, adopts the stainless steel reactor that internal diameter is 10mm, 10 milliliters of loaded catalysts, 500 ℃ of reaction temperatures, reaction pressure 0.5MPa, mass space velocity 5 hours
-1, raw material adopts C4 ~ C6 mixing lower carbon number hydrocarbons, specifically forms in Table 1.
Product is analyzed respectively after gas-liquid separation, and gas-phase product adopts Agilent gas-chromatography 6820, Al
2o
3pillar, hydrogen flame detector; Liquid product adopts Agilent gas-chromatography 6820, FFAP pillar, hydrogen flame detector.Analysis result normalization.When being 20 and 60 hours, the reaction time the results are shown in Table 2.
[comparative example 7]
With [embodiment 4], investigate the performance of [comparative example 1 ~ 6] catalyst.
Table 1
| Raw material components | Butane | Butylene | Pentane | Amylene | Hexane | Hexene | Other |
| Percentage composition (% by weight) | 1.7 | 2.2 | 25.3 | 44.6 | 7.6 | 8.6 | 10.0 |
Table 2
Therefrom can find out, with simple employing steam treatment, and adopt the catalyst of steam treatment loading metal to compare, the catalyst of preparing through steam treatment, acid treatment and carried metal has been obtained better initial conversion and aromatics yield in aromatization of low carbon hydrocarbon course of reaction, and reaction stability has obtained obvious raising.
[embodiment 5]
On the device of [embodiment 4], adopt C4 ~ C6 mixing lower carbon number hydrocarbons, as raw material, [embodiment 2] prepared catalyst is carried out to stability examination.
Examination condition is: synthesis under normal pressure, weight space velocity 1.2 hours
-1, 450 ~ 580 ℃ of reaction temperatures.Appraisal result is in Table 3.
Table 3
| Reaction time, hour | Aromatics yield, % by weight |
| 100 | 50.3 |
| 200 | 49.2 |
| 300 | 49.0 |
| 400 | 48.7 |
| 500 | 48.7 |
| 600 | 48.3 |
| 700 | 47.9 |
Therefrom can find out, catalyst single pass life is greater than 700 hours, aromatics yield 48 % by weight.
Claims (8)
1. a preparation method for aromatization of low carbon hydrocarbon catalyst, comprises the following steps:
A) 50 ~ 90 parts of ZSM-5 molecular sieves and 10 ~ 50 parts of binding agents are kneaded and formed, obtain preformed catalyst precursor mixture I;
B) by mixture I, in normal pressure, temperature, be that 200 ~ 700 ℃, air speed are 0.1 ~ 20 hour
-1water Under steam treated 0.1 ~ 40 hour, obtains precursor II;
C) precursor II being placed in to the acid solution that concentration is 0.1 ~ 5 mol/L, is to process 0.1 ~ 24 hour under 20 ~ 95 ℃ of conditions in temperature, obtains precursor III;
D) by infusion process, to the load of precursor III, be selected from least one element in VIII, IIBHuo IIIA family, obtain described aromatization of low carbon hydrocarbon catalyst; Wherein, load capacity is 0.1 ~ 10% of precursor III weight.
2. the preparation method of aromatization of low carbon hydrocarbon catalyst according to claim 1, is characterized in that described binding agent is selected from least one in aluminium oxide or boehmite.
3. the preparation method of aromatization of low carbon hydrocarbon catalyst according to claim 1, is characterized in that steam treatment temperature is 300 ~ 600 ℃, and air speed is 1 ~ 18 hour
-1, the processing time is 1 ~ 30 hour.
4. the preparation method of aromatization of low carbon hydrocarbon catalyst according to claim 1, is characterized in that described acid is selected from least one in oxalic acid or nitric acid.
5. the preparation method of aromatization of low carbon hydrocarbon catalyst according to claim 1, the concentration that it is characterized in that acid solution is 0.2 ~ 4 mol/L, and acid treatment temperature is 30 ~ 85 ℃, and the time is 1 ~ 20 hour.
6. the preparation method of aromatization of low carbon hydrocarbon catalyst according to claim 1, it is characterized in that VIII family element is selected from least one in Fe, Co or Ni, IIB family element is selected from least one in Zn or Cd, and IIIA family element is selected from least one in Al or Ga.
7. the preparation method of aromatization of low carbon hydrocarbon catalyst according to claim 1, the load capacity that it is characterized in that being selected from least one element in VIII, IIBHuo IIIA family is 0.5 ~ 8% of precursor III weight.
8. the preparation method of aromatization of low carbon hydrocarbon catalyst according to claim 1, is characterized in that the silica alumina ratio SiO of ZSM-5 molecular sieve
2/ Al
2o
3be 20 ~ 300.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106552663A (en) * | 2015-09-24 | 2017-04-05 | 中国石油天然气股份有限公司 | Catalyst for aromatization of straight-run naphtha and preparation method thereof |
| CN109465022A (en) * | 2018-10-16 | 2019-03-15 | 上海兖矿能源科技研发有限公司 | Low-carbon hydrocarbon aromatization catalyst and preparation and application suitable for Fischer-Tropsch synthesis oil |
| CN112705249A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Preparation method of catalyst for producing aromatic hydrocarbon, catalyst and application thereof |
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| US6084142A (en) * | 1998-05-12 | 2000-07-04 | Phillips Petroleum Company | Method of making an improved zeolite catalyst, a product from such method, and the use thereof in the conversion of hydrocarbons |
| CN1310047A (en) * | 2000-02-24 | 2001-08-29 | 中国石油化工集团公司 | Method of raising the stability of catalyst for benzene and ethylene alkylation |
| CN1586721A (en) * | 2004-07-30 | 2005-03-02 | 大连理工大学 | Catalyst for C4 liquefied petroleum gas aromatization and its preparing method |
| CN102464538A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Low-carbon hydrocarbon aromatization method |
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Patent Citations (5)
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| CN1070847A (en) * | 1992-10-15 | 1993-04-14 | 大庆石油学院 | Gallium, zinc, platinum modified HZSM-5 catalyst for aromatization of low carbon chain hydrocarbons |
| US6084142A (en) * | 1998-05-12 | 2000-07-04 | Phillips Petroleum Company | Method of making an improved zeolite catalyst, a product from such method, and the use thereof in the conversion of hydrocarbons |
| CN1310047A (en) * | 2000-02-24 | 2001-08-29 | 中国石油化工集团公司 | Method of raising the stability of catalyst for benzene and ethylene alkylation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106552663A (en) * | 2015-09-24 | 2017-04-05 | 中国石油天然气股份有限公司 | Catalyst for aromatization of straight-run naphtha and preparation method thereof |
| CN109465022A (en) * | 2018-10-16 | 2019-03-15 | 上海兖矿能源科技研发有限公司 | Low-carbon hydrocarbon aromatization catalyst and preparation and application suitable for Fischer-Tropsch synthesis oil |
| CN112705249A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Preparation method of catalyst for producing aromatic hydrocarbon, catalyst and application thereof |
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